Preparation of baked products



United States Patent 3,394,009 PREPARATION OF BAKED PRODUCTS William H. Knightly, Wilmington, Del., assignor to Atlas Chemical Industries, Inc., Wilmington, Del., a corporation of Delaware No Drawing. Filed July 24, 1964, Ser. No. 385,036 6 Claims. (CI. 99-91) ABSTRACT OF THE DISCLOSURE A softener and mold inhibitor for baked products comprising a composition containing esters of a lower monocarboxylic acid and a polyhydric alcohol incorporated into the ingredients of the dough or batter of the product prior to baking.

This invention relates to an improvement in the preparation of baked products. In particular, this invention relates to an improved liquid softening agent and mold inhibitor for baked products.

It is current practice in the preparation of yeastleavened baked products, such as bread, rolls and sweet doughs, to incorporate a softener or anti-stalant in the dough and also a fungistat to inhibit microbiological growth in the yeast-leavened products. The softeners most generally used are mixtures of monoand diglycerides which are plastic materials and are difficult to handle, measure and thoroughly disperse in the dough. Previous attemps to use liquid softeners have been unsuccessful because of adverse effects on dough condition and the resulting baked product.

In addition to the softeners, fungistatic agents are also incorporated into yeast-leavened baked goods. The fungistatic agents most generally used are calcium or sodium propionates. These propionate salts are effective in inhibiting microbiological growth, but also adversely alfect the functioning of the yeast as demonstraated by increased proof time and in some instances poorer grain and volume.

In view of the long periods of time which may expire between the preparation and consumption of baked goods, such as cakes and cupcakes, it is considered desirable in some instances to incorporate fungistats in this type of baked product. It is important that the fungistatic agent not have a substantial adverse effect on the quality of the final baked product.

It is an object of this invention to provide an improvement in the preparation of baked products.

It is another object to provide a liquid softening agent and fungistat which is easy to handle, is readily incorporated into dough and does not adversely affect proof time, grain and volume of yeast-leavened baked products.

Other objects and purposes of this invention will be apparent to those skilled in the art in view of the description which follows.

It has been discovered that lower monocarboxylic acid esters of glycerin and isosorbide are elfective softening agents and fungistats when incorporated into baked products. These lower monocarboxylic acid esters are generally liquids which are easy to measure and handle. Since these esters are liquids, they are readily incorporated into the dough or batter of baked goods prior to baking, and they do not adversely affect dough conditioning, i.e. the handling and machining characteristics of the dough. The esters also function as fungistats and 3,394,009 Patented July 23, 1968 do not adversely affect proof time at the recommended levels of use as do the propiona'te salts which are currently used as fungistats. In addition, the lower monocarboxylic acid esters of glycerin and/or isosorbide do not adversely affect the grain and volume characteristics of the resulting baked products.

The softeners and fungistats useful in this invention comprise complete and partial esters of glycerin and isosorbide and their mixtures. Though the lower monocarboxylic acid esters may be used in relatively pure form, generally in preparing the esters mixtures are formed, and it is convenient to use the mixture and thereby avoid a purification procedure. As used in this specification and the claims which follow, the term lower monocarboxylic acid esters of glycerin. includes mono-, diand triesters and mixtures thereof, and the term lower monocarboxylic acid esters of isosorbide" includes monoand diesters and mixtures thereof.

The term lower monocarbojylic acids" as used in this specification and the claims which follow includes those monocarboxylic acids having from 2 to 7 carbon atoms. Examples of monocarboxylic acids which may be used to esterify the glycerin or isosorbide are acetic, propionic, butyric, valeric, caproic, sorbic and benzoic. It is particularly preferred to use propionic, sorbic or benzoic acids, for these acids provide especially effective fungistatic properties. Propionic acid has been found to be particularly effective. In addition to using the acids, their equivalent halides, anhydrides and esters may also be used to carry out the esterification. Conventional esterification procedures may be used to prepare the glycerin and isosorbide esters, and therefore their preparation does not have to be described in detail.

The compositions of the present invention are usually incorporated into baked products in amounts which are sufficient effectively to inhibit the growth of mold during storage for durations of about a week and also sufficient to preserve the softness of the product during storage. In general, amounts of the lower monocarboxylic acid ester as little as about 0.04% based on the weight of the flour contained in the product are sufiicient for effective mold growth inhibition in the product. Since greater amounts of the compositions of the present invention are required to impart the desired softening or anti-staling characteristics to the baked product, the critical concentrations of the said composition in the baked product are accordingly determined by the amounts required for that purpose. In general, in yeast leavened products, from about 0.2% to about 1.0% of the composition based upon the weight of the flour in the product is sufficient to impart both mold growth inhibition and softness or antistaling properties to the baked product; in baked products which do not contain yeast however, the compositions of the present invention are usually used in amounts within a range of about 0.8% to about 20.0% based upon the weight of the flour in the baked product.

The following examples demonstrate the preparation of propionate esters of glycerin and isosorbide and their use as softening agents and fungistatic agents.

About 460 g. of glycerin (5 moles) were placed in a 3-necked flask equipped with a mechanical stirrer, condenser, thermometer and dropping funnel. 1250 g. (9.65 moles) of propionic anhydride was added dropwise at a temperature of 125130 C. over a period of 2.25 hours. The reaction mixture was heated for 18 hours at C. after the propionic anhydride had been added. Propionic acid was stripped off under reduced pressure,

3 and the resulting mixture was distilled over a inch vigreux column. The following four liquid cuts were collected:

The sponges were prepared by dissolving the yeast in a portion of the water, and this composition was added Pot Temp. Vap. Temp. Sap. OII Acid Grams Yield,

( C.) C.) No. No. No. Collected Percent Cut #1"-.- 110-115 98-100 542 298.5 7.45 170 18.2 Cut #2. 110 107 548 274 1. 07 135 14.1 Cut#3. 114-121 105110 501 244 0.05 243 25.4 Cut #4 117-120 105-110 570 190 0.30 300 38.1 Residue 501 s 0. 00 40 4.2

The approximate composition of each fraction was as to a mixer along with flour, yeast food and the balance follows: 15 of the water. These ingredients were mixed for about 3 Cut mono and 95% dipropionatc minutes and thereafter fermented for about 4.5 hours. Cut #2 1O0% dipropionate The fermented spongeswere returned to the mixer and Cut mono and and 98% dipropionam all of the dough ingredlents were added. The dough- Cut and 30% tripropionate sponge mixtures were mlxed to full development (usualt ly about 11 to 13 minutes), fermented for 20 minutes, Example II-PreParah0h of lsosofhlde dlpfoplohflte divided, allowed a 10 minute proof, sheeted, molded, A three iiter 3 necked flask ekuipped with a stirrer) sealed and placed into bread pans. Then the dough was thermometer, dropping funnel and a reflux condenser was Proofed at about and 85% relative humidity in Charged with 4383 (3 moles) of iSOsOi-hidc and 2 the usual manner to template height and baked for about of p-toluene-sulfonic acid. The isosorbide was heated to 20 mhmtes at 2 C, and then 858 g (6 moles Pius excess) f Prior to baking, the bread dough was evaluated for propionic anhydride were added dropwise with stirring fiough Cohdltlohlhg Properties and Proof time- After over a 90 minute period The tempfirature during the mg, the bread was evaluated for volume, grain and softadtiitioh Varied between c Th ft the teac ness. Softness studies on half-inch thick bread slices were tion mixture was heated for 10 hours at 100 C. and then Carried out Over 3 Period of 6 y using a gelometel to f 4 hours at 55 CI, afteit which pi-opioniC acid determine softness. The gelometer value represents the and excess propionic anhydride were stripped off under number of grams of Shot required to depress the gelometef vacuum plunger a given distance (4 mm. in these evaluations) The resulting liquid product was treated with 10 g. of into the bread Sliceactivated carbon and distilled through a 10 inch vigreux h softness data are given for the first y y column at l35-138 c. and 0.5 mm. pressure. 540 g. of lowmg baking), second to fourth y and fifth to seve t isosorbide dip opionate was b[aind day. Th6 data obtained On the SBCOIld t0 fOlllth day are E 1 In P of b d t considered to be of greatest significance. Readings obg y g g reflection of the extent of baking, while those obtained The following bread formula and P r s W on the fifth to seventh day are considered of less imlltihled t0 Wilhlate Several Propionate esters as bread portance since little bread remains to be consumed this softening agents according to the sponge-dough method: long ft baking s percent (fl r as 100% Using the glyceryl propionate esters of Example I and Flour 65 the isosorbide dipropionate of Example 11 as softening Water Variable agents, the baking of three loaves of bread with each Yeast 2.5 S ftening agent yielded the following results: Yeast food 0.5

Dough Proof Volume (cc.) Gelometer Values Grain Softening Agent Conditioning Time (min) A B 0 Avg 1 Day 4 Days 6 Days 1 Day 4 Days 6 Days Control (110 soitener) Very good 75 2,600 2,625 2,050 2,625 215 262 385 Very good. Cut #1 do. 05 2,700 2,730 2,750 2,727 202 245 373 Do. Cut#2 05 2,775 2,750 2,735 2,753 100 243 304 Good. Cut#3 2,650 2,675 2,675 2,667 209 245 371 Very good. Gut#4 04 2,700 2,075 2,700 2092 207 249 353 D0.

(2 Days) (2 Days) Isosorbide Dipropionatek. Good 73 2, 650 2, 675 2, 660 2,663 241 358 375 Good Good"... Good. Control (no s0ltenor) Very good. 00 2,500 2,550 2,525 2, 525 201 398 419 Fair V. Good Very good.

1 The controls contained 0.25% calcium propionate bread preservative. Z The isosorbide dipropionate and glyceryl propionatcs were evaluated in separate tests.

1 57% of the total water was added to the sponge and 43% was added to the dough. The total amount of water used varied depending upon the flour absorption properties. The amount of Water required was determined by a farinograph method which is described in Cereal Laboratory Methods c0111- piled by American Association of Cereal Chemists, 6th ed., pp. 132-139.

These results demonstrate that the propionate esters definitely improved bread volume and bread softness. In addition, the propionate esters did not adveresely affect proof time, dough conditioning or the bread grain.

Example IV The procedures and evaluations of Example III were repeated using 0.5% per flour weight of the softening agents instead of 0.25 as in Example III. The results are reported in the following table:

Then 99.8 g. of whole eggs and 50 g. of water were added, and the mixing was continued at speed No. 2 for Dough Proof Volume (00.) Gelometer Values Grain Softening Agent Conditioning Time (min) A B Avg. 1 Day 4 Days 6 Days 1 Day 4 Days 6 Days Control (no softener) Very good 105 2,525 2, 525 2, 515 2,522 231 342 392 Fair air Good Cut #1 Goo 82 2,625 2, 600 2, 615 2, 613 236 335 346 .do .do Fair.

80 2, 550 2, 550 2, 565 2,555 234 318 361 Good ood. Good. do- 80 2, 550 2, 565 2, 560 2, 558 210 322 337 Fair "do" Do. Cut #4 .do. 82 2, 525 2, 550 2, 550 2, 542 225 312 330 Gooddo Do. Isosorblde Dipropionate "do 68 2,750 2,750 2,735 2,740 208 310 382 -do V. goo Do. Control (no softener) Very good 110 2,475 2,450 2,500 2,475 233 411 481 do Fair Fair.

1 The controls contained 0.5% calcium propionate bread preservative.

2 The isosorbide dipropionate and glyceryl propionates were evaluated in separate tests.

These results corroborate the improvements in the preparation of bread which were demonstrated in Example III.

Example V The glyceryl propionate and isosorbide propionate addianother 2 minutes. Upon completion of the mixing, 2 eight inch pans were filled with 350 g. of batter each and were baked at 350 F. for 27 minutes.

The results were as follows:

Shortening Cont aining Cake Batter Symmetry Cake Cake Batter Sp. G. of Rise Vol. (ec.) Grain Isosorbide Monopropionate... Tl1in 0.92 Good 2,090 Good. 5% Glyceryl Dipropionate do 0. 94 ..do Do.

PRESERVATIVE EFFECT Amount (percent F.W.)

Fungistatic-Agent 3 Days 8 Days 10 Days No mold. Moldy 0.

Control (no fungistat) Out #1 do N3 mo1d No mold.

These results clearly demonstrate the fungistatic effect of the glyceryl propionates and isosorbide dipropionates.

Example VI Hydrogenated vegetable oil shortening containing 5% by weight isosorbide monopropionate in one instance, and 5% by weight glyceryl dipropionate in the other, was used to prepare a devils food cake. The following formulation was used:

Grams Cake flour 181.6 Sugar 236.1 Baking soda 3.4 Breakfast cocoa 36.3 Nonfat dry milk 31.7 Salt 5.66 Baking powder 9.06

Hydrogenated vegetable oil shortening containing 5% propionate Water The above listed ingredients were added to a mixing bowl and mixed for 3 minutes at speed No. 1 in a Hobart mixer. 51 g. of water was then added and the mixing continued at speed No. 2 for 2 minutes.

These results demonstrate that the glyceryl dipropionate and isosorbide monopropionate functioned as an emulsifier for the cake formulation. These esters would also contribute their fungistatic properties to the cake which helps to preserve the cake.

Example VII Using the bread formulation and procedures of Example III, glyceryl monobenzoate was incorporated into the formulation and was tested as a softening agent and fungistatic agent. The glyceryl monobenzoa'te was used at a level of 0.5% by weight of flour. The bread which was produced had good volume, better softness than a control containing no softening agent, and was rated as good with respect to anti-mold performance.

Example VIII Using the bread formulation and procedures of Example III, glyceryl monosorbate is incorporated into the formulation and tested as a softening agent and fungistatic agent. The glyceryl monosorbate may be used at a level of 0.25% by weight of flour. The resulting bread product has good volume, good softness and very good anti-mold performance.

Having completely described this invention, what is claimed is:

1. In the preparation of a baked product, the improvement which comprises the steps of incorporating into the wet ingredients thereof prior to baking from about 0.2 percent to about 20.0 percent by weight, based upon the weight of the flour in said product, of an antistalent and antimycotic composition consisting essentially Of esters of a lower monocarboxylic acid selected from the group consisting of sorbic acid, benzoic acid and propionic acid and a polyhydric compound selected from the group consisting of glycerine and isosorbide and then baking the resultant product.

2. The improvement of claim 1 in which the baked product to be prepared is yeast-leavened.

3. The improvement of claim 2 in which the polyhydric compound is glycerin.

4. The improvement of claim 3 in which the lower monocarboxylic acid ester is a propionate.

5. The improvement of claim 4 in which the glycerin ester is glyceryl dipropionate.

6. The improvement of claim 4 in which the glycerin ester is glyceryl tripropionate.

(References on following page) References Cited UNITED STATES PATENTS 8 Jackson et a1 9992 X Geisler 99118 Buddemeyer et a1. 9992 X Colby 99118 X RAYMOND N. I ONES, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,394 ,009 July 23 1968 William H. Knightly It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 13, after "alcohol" insert is line 59, "demonstraated" should read demonstrated Column 2, line 19, "m0nocarbojylic should read monocarboxylic between lines 59 and 60, insert as a heading, Example I.-

Preparation of propionate esters of glycerin Column 3, line 22, "ekuipped" should read equipped Signed and sealed this 24th day of February 1970.

(SEAL) Attest:

Edward M. Fletcher, Jr. WILLIAM E. SCHUYLER, JR.

Attesting Officer Commissioner of Patents 

